Polyphenylene sulfide resin compositions

ABSTRACT

A polyphenylene sulfide resin composition which comprises 100 parts by weight of a polyphenylene sulfide resin (A) and, compounded therewith, 1 to 100 parts by weight of glass fibers (B) having a single-fiber diameter of 12 μm or lager and has a crystallization temperature during cooling of 205° C. or lower. Also provided is a polyphenylene sulfide resin composition which comprises 100 parts by weight of a polyphenylene sulfide resin (A) and, compounded therewith, 1 to 100 parts by weight of glass fibers (B) having a single-fiber diameter of 10 to 12 μm, excluding 12 μm, has a crystallization temperature during cooling of 205° C. or lower and a chloroform-extractable content of 0.5 wt. % or lower, and gives a 2 mm-thick molded product which has a transmittance of 15% or higher for laser beam having a wavelength of 940 nm and a heat distortion temperature of 230° C. or higher under a load of 1.82 MPa.

FIELD OF THE INVENTION

The present invention relates to a polyphenylene sulfide resincomposition, and more particularly, a polyphenylene sulfide resincomposition capable of obtaining an excellent laser weldability and heatresistance without lowering the degree of freedom for design of a moldedproduct, even when used for the molded product of the laser beamtransmitting side in a laser welding method.

DESCRIPTION OF BACKGROUND ART

Polyphenylene sulfide resin composition is widely used for electricaland electronic components and automobile parts because it is providedwith well-balanced properties such as excellent mechanical properties,heat resistance, chemical resistance and thin fluidity.

Conventionally, in case of resin molded product of complicated shape, aplurality of separated parts are molded beforehand, then these parts areintegrally bonded to obtain a product of complicated shape. As means forintegrally bonding a plurality of parts in such a manner, bonding byadhesive agent, mechanical bonding with bolt or the like, bonding byexternal heat welding such as laser welding, hot plate welding, andbonding by friction heat welding such as vibration welding, ultrasonicwelding have been used. Among these means, it is difficult to obtainhigh bonding strength by the bonding with bonding agent, and themechanical bonding requires more cost and labor and, moreover, causesweight increase. However, bonding by external heat welding or frictionheat welding has been increasingly used in recent years, because itdoesn't use extra material such as adhesive agents or bolts and,moreover, it doesn't causes problems such as an environmental pollution,weight increase.

Among the aforementioned external heat welding, the laser weldingmethod, in particular, has an advantage of being performed easily. Thelaser welding method for two resin molded products, as disclosed forinstance in the patent document 1, is executed by irradiating laser beamfrom one of superposed two molded products to the other. The laser beamtransmits through the molded product of irradiating side to be absorbedinto the molded product of the other side and melts the resin to fuiseand bond both molded products therebetween. Therefore, it is essentialfor laser welding method that the laser beam transmits through themolded product of irradiation side into the other molded product.Consequently, two molded products can not be bonded, or a sufficientbonding strength can not be obtained, if a resin material with low laserbeam transmittance is used for the molded product into which the laserbeam transmits.

Whereas, the aforementioned polyphenylene sulfide resin of highcrystallinity is characterized by significantly low laser beamtransmittance. Therefore, in case of using polyphenylene sulfide resincomposition for a molded product of laser beam transmitting side in thelaser welding method, it has been necessary to thin the molded productso as to transmit the laser beam. Consequently, in case of bondingpolyphenylene sulfide resin composition by the laser welding method,there has been a problem that degree of freedom for design of the moldedproduct becomes inevitably low.

Patent document 1: JP S60-214931 A1

BRIEF SUMMARY OF THE INVENTION

The present invention has a main object of resolving the aforementionedproblems of polyphenylene sulfide resin composition, and providing apolyphenylene sulfide resin composition capable of obtaining excellentlaser weldability and heat resistance without lowering the degree offreedom for design of the molded product, even when used for the moldedproduct of laser beam transmitting side in the laser welding method.

Another object of the present invention is to provide a polyphenylenesulfide resin composition with excellent low warpage properties thatreduces the generation of warpage when it is molded.

Still other objects of the present invention shall be disclosed by theconcrete descriptions hereinafter.

The polyphenylene sulfide resin composition of the present invention forachieving the aforementioned main objects is characterized in that 100parts by weight of a polyphenylene sulfide resin (A) is compounded with1 to 100 parts by weight of glass fiber (B) having a monofilamentdiameter of 12 μm or larger and crystallization temperature on coolingis 205° C. or lower. It should be noted that “weight” means “mass”herein.

In the present invention, laser transmittance of a polyphenylene sulfideresin composition and heat resistance can be improved, by compouning 1to 100 parts by weight of glass fiber (B) having a monofilament diameterof 12 μm or larger with respect to 100 parts by weight of polyphenylenesulfide resin (A) and keeping the crystallization temperature on coolingis 205° C. or lower. Therefore, an excellent laser weldability can beexhibited, if this polyphenylene sulfide resin composition is used forthe molded product of laser beam transmitting side in the laser weldingmethod. In addition, as the laser weldability is excellent, the degreeof freedom for design can be improved when polyphenylene sulfide resincomposition is injection molded.

Moreover, it is preferable to make chloroform-extractable content to be0.5 weight % or lower for the polyphenylene sulfide resin composition ofthe present invention. The laser weldability can be further improved byreducing this chloroform-extractable content. Besides, it is possible tomake a 2 mm-thick molded product with a laser beam transmittance of 15%or higher at a wavelength of 940 nm and to provide a heat resistancewith a heat distortion temperature of 230° C. or higher under a load of1.82 MPa.

Glass fiber (B) to be compounded with polyphenylene sulfide resincomposition of the present invention has a monofilament diameter of 12μm or larger and preferably a thick monofilament diameter of 15 μm orlarger, however, even the monofilament diameter of the glass fiber isless than 12 μm, laser welding and heat resistance as excellent asmentioned above can be obtained by adopting the following composition,if the monofilament diameter is 10 μm or larger.

In short, another polyphenylene sulfide resin composition of the presentinvention compounded with the aforementioned glass fiber ischaracterized in that 100 parts by weight of polyphenylene sulfide resin(A) is compounded with 1 to 100 parts by weight of glass fiber (B)having a monofilament diameter of 10 μm or higher but less than 12 μmand the crystallization temperature on cooling is 205° C. or lower and achloroform-extractable content is 0.5 weight % or lower, and furthermore, the laser beam transmittance is 15% or higher at a wavelength of940 nm when the molded product is 2 mm-thick and the heat distortiontemperature is 230° C. or higher under a load of 1.82 MPa.

For the polyphenylene sulfide resin composition of the presentinvention, in addition to the aforementioned component (A) and (B), itis advantageous to be compounded furthermore with 1 to 200 parts byweight of filler (C) having a refractive index of 1.6 to 1.8 and/orfiller (D) having a refractive index of less than 1.6 or more than 1.8and an average particle diameter of 30 μm or larger. By compounding suchfillers, it is possible to inhibit the warpage of the injection moldedproduct and moreover to improve the heat resistance and mechanicalstrength.

As for the aforementioned filler (C), fibrous or plate alumina hydrate(C1), and/or fiber or granular H glass (C2) are preferable. Besides, forthe aforementioned filler (D), glass flake (D1) and/or glass bead (D2)are preferable.

In addition to the aforementioned component (A) and (B), thepolyphenylene sulfide resin composition of the present invention may becompounded with 0.1 to 200 parts by weight of one or plural kinds ofamorphous resin selected from polyamide-imide resin (E1), polyetherimideresin (E2), polyethersulfone resin (E3) and polysulfone resin (E4). Bycompounding this amorphous, laser weldability and warpage properties canfurther be improved.

Also, in addition to the aforementioned component (A) and (B), thepolyphenylene sulfide resin composition of the present invention mayfurther be compounded with 0.01 to 3 parts by weight of silane compound(F) and/or 0.01 to 3 parts by weight of anti-oxidant(G). By compoundingthem, not only the laser weldability and warpage properties but also themechanical strength can further be improved.

Moreover, in addition to the aforementioned component (A) and (B), thepolyphenylene sulfide resin composition of the present invention mayfurther be compounded with 0.5 to 20 parts by weight of elastomer (H).By compounding this elastomer (H), cold and heat resistance or impactresistance of the polyphenylene sulfide resin composition can beimproved.

The polyphenylene sulfide resin composition of the present invention canexhibit an excellent weldability as a molded product of laser beamtransmitting side, when it is made into a composite molded product bybonding with other resin molded product by the laser welding method, inparticular, it shows a remarkable effect in case where the transmittingsection thickness of welding site is 5 mm or lower. The other resin forthe composite molded product may be polyphenylene sulfide resin, orother than polyphenylene sulfide resin composition.

DETAILED DESCRIPTION OF THE INVENTION

The polyphenylene sulfide (hereinafter referred to as PPS) resincomposition of the present invention is characterized in that 100 partsby weight of PPS resin (A) is compounded with 1 to 100 parts by weightof glass fiber (B) having a monofilament diameter of 12 μm or largerand, moreover, the crystallization temperature on cooling as PPS resincomposition is 205° C. or lower. Preferably, this PPS resin compositionhas a chloroform-extractable content of 0.5 weight % and, laser beamtransmittance is 15% or higher at a wavelength of 940 nm when it is madeinto a 2 mm-thick molded product, and a heat distortion temperature is230° C. or higher under a load of 1.82 MPa. Besides, in case where PPSresin composition is compounded with glass fiber (B) having amonofilament diameter of 10 μm or larger but less than 12 μm, it may bemade so that the crystallization temperature on cooling is 205° C. orlower and the chloroform-extractable content is 0.5 weight % or lower,and the laser beam transmittance is 15% or higher at a wavelength of 940nm when it is made into a 2 mm-thick molded product, and the heatdistortion temperature is 230° C. or higher under a load of 1.82 MPa.

The PPS resin composition of the present invention can be made toexhibit extremely excellent laser weldability, by adopting theaforementioned composition. In order to keep the crystallizationtemperature of a PPS resin on cooling at 205° C. or lower as mentionedabove, PPS resin composition of low crystallization temperature oncooling may be used. Also, a PPS resin of low chloroform-extractablecontent may be used for making the chloroform-extractable content of thePPS resin composition 0.5 weight % or lower. Now, PPS resins to be usedfor the present invention and components to be compounded with this PPSresin shall be described hereinafter.

(1) PPS Resin

The PPS resin (A) used for the present invention is a polymer having arepeating unit shown by the following structural formula, and preferablythe polymer has 70 mol % or more, in particular, 90 mol % or more ofrepeating unit shown by the structural formula, to obtain a favorableheat resistance.

Besides, the parts less than 30 mol % of a repeating unit of the PPSresin can be composed of a repeating unit and the like having thefollowing structure.

A PPS resin composition of low crystallization temperature on coolingmay be used for keeping the crystallization temperature of the PPS resincomposition on cooling within a range prescribed by the presentinvention. Preferably, PPS resins having a crystallization temperatureon cooling of 200° C. or lower, more preferably, 195° C. or lower areused. The lower limit of the crystallization temperature on cooling ispreferably 170° C. or higher from a perspective of heat resistance. Thecrystallization temperature on cooling of PPS resin tends to decrease asthe molecular weight increases, namely as the melt flow rate(hereinafter referred to as MFR) decreases. Consequently, MFR of the PPSresins to be used is 500 g/10 min or lower, preferably 350 g/10 min orlower and, especially preferably 200 g/10 min or lower. The lower limitof MFR is preferably 30 g/10 min or higher from a perspective offluidity loss. It should be noted that MFR is a value measured under aload of 5 kg after having dried 5 g of PPS resin powder at 130° C. for 3hours and melted at 315.5° C. to stay for 5 min, conforming toJIS-K7210.

If a co-polymer of meta-phenylene sulfide unit and para-phenylenesulfide unit are used as PPS resin, the melting point lowers accordingto the copolymerized amount of the meta-phenylene sulfide unit,permitting the crystallization temperature on cooling to lower.Furthermore, as another method for lowering the crystallizationtemperature on cooling of PPS resin, a method can be cited that uses apolyhaloaromatic compound of trihalo or more in combination with adihaloaromatic compound when the polymerization starts. A branchedpolymer or a crosslinked polymer is formed by this method to lower thecrystallization temperature on cooling.

In the present invention, a PPS resin having sufficiently lowchloroform-extractable content may be used for keeping thechloroform-extractable content of the PPS resin composition within theprescribed range. More specifically, the chloroform-extractable contentof PPS resins is preferably 0.6 weight % or lower, and more preferably0.4 weight % or lower. The MFR of PPS resin is preferably 500 g/10 minor lower, and especially preferably 300 g/10 min or lower, becausegenerally the chloroform-extractable content tends to decrease as themolecular weight increases, namely as the MFR lowers.

Besides, as for a method for reducing the chloroform-extractable contentof PPS resin, a post treatment such as an organic solvent treatment,acid treatment or heat treatment of PPS resin after polymerization maybe executed. The organic solvent treatment, in particular, ispreferable, because it has a significant effect for lowering thechloroform-extractable content. The heat treatment is executedpreferably under inactive atmosphere, in order to avoid the decrease oflaser weldability by the discoloration of PPS resin. However, even ifthe heat treatment is executed under inactive atmosphere, a heattreatment at high temperature for long period of time should be avoided,because it will color the PPS resin to cause deterioration of the laserweldability. The heating temperature is 120 to 220° C., and preferably150 to 200° C. Besides, the heating time is 5 to 20 hours, andpreferably 10 to 15 hours.

(Polymerization of PPS Resin)

In general, PPS resin can be produced by using the method for obtainingpolymers of relatively low molecular weight as described in the JPS45-3368 B1, or of relatively heavy molecular weight as described in theJP S52-12240 B1 and the like. The difference between the former and thelatter is the presence/absence of alkali metal carboxylate as apolymerization auxiliary in the polymerization system.

In the former, since alkali metal carboxylate is not added into thepolymerization system and the degree of polymerization does notincrease, the molecular weight is relatively low and the crystallizationtemperature on cooling increases. Moreover, since the polymer contains alot of impurities and the chloroform-extractable content increases,discoloration by heat of the compositions or the molded products duringthe manufacturing results in the reduction of the laser weldability. Incase of the latter, since alkali metal carboxylate is added into thepolymerization system and the degree of polymerization increases, themolecular weight is relatively large and the crystallization temperatureon cooling decreases, making it relatively easy to keep thecrystallization temperature on cooling within the range of the presentinvention. Also, since it contains less impurities, thechloroform-extractable content decreases, permitting to inhibit thediscoloration by heat and present an excellent laser weldability.

The latter method can relatively easily satisfy the condition prescribedin the present invention; however, it is necessary to adjust reactionconditions so that the PPS resin satisfies prescribed range of thepresent invention. Nevertheless, it is possible to adjust the PPS resinfluidity and others by using in combination with the PPS resin accordingto the former method.

Besides, in polyphenylene sulfide copolymer where methaphenylene-sulfideunit is introduced into a PPS resin having para polyphenylene sulfideunit, the crystallization temperature on cooling is low compared with apolymer having paraphenylene-sulfide unit alone, as mentioned above. Asfor the copolymerization ratio (molar fraction) of these units, themethaphenylene-sulfide unit is preferably 1 mol % or higher to the totalof methaphenylene-sulfide units and paraphenylene-sulfide units, andmore preferably, 3 mol % or higher. The upper limit is preferably lessthan 15 mol % from the perspective of heat resistance. As forcopolymerization mode, any of random copolymerization and blockcopolymerization is acceptable; however, random copolymerization ispreferable from a perspective of balance of laser weldability and heatresistance.

Moreover, also the method for using in combination with polyhaloaromaticcompound of trihalo or more when the polymerization starts can lower thecrystallization temperature on cooling as mentioned above. In this case,as for the copolymerization amount of polyhaloaromatic compound, thepolyhaloaromatic compound is preferably 0.01 mol % or higher to thetotal of polyhaloaromatic compound and dihaloaromatic compound, morepreferably 0.04% or higher and still more preferably 0.06% or higher.The upper limit is preferably 0.1 mol % or lower from a perspective offluidity loss. Concrete examples of polyhaloaromatic compound includes1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-tribromobenzene,1,2,4-tribromobenzene, and the like. Besides, it is also possible to useactivated hydrogen-containing halogen aromatic compounds and halogenaromatic nitro compounds in combination with dihaloaromatic compounds.

(Post Treatment)

In the present invention, post treatments of PPS resin such as heatingtreatment, washing with an organic solvent, acid treatment or carboxilicmetal salt aqueous solution treatment are effective as means forimproving the laser weldability by lowering PPS resin crystallizationtemperature on cooling and the chloroform-extractable content, or forimproving mechanical properties.

Among the aforementioned PPS resin post treatment methods, heatingtreatment can be executed for the purpose of removing impurities, namelychloroform extracts, which cause discoloration. However, an excessiveheating treatment is not preferable, because it provokes oxidationcoloring that deteriorates the laser weldability. Concrete heatingtreatment conditions are as mentioned below.

In short, usually, the heating treatment of PPS resin is executed in arange of 200 to 260° C., however heating at such a high temperaturecauses oxidation coloring. Therefore, in the present invention, theheating treatment is preferably executed in a temperature range of 120to 220° C., more preferably in a temperature range of 150 to 200° C.Also, the heating time is preferably 5 to 20 hours, more preferably 10to 15 hours. As for the heating treatment atmosphere, it is preferableto heat under an inactive atmosphere such as nitrogen atmosphere,because the laser weldability is significantly deteriorated due tooxidation coloring under an oxygen atmosphere.

Organic solvent washing of PPS resin is preferable because it permits toremove impurities causing the discoloration, namely chloroform extracts.Organic solvents to be used for washing PPS resin are not specificallylimited, provided that they do not have any function of decomposing PPSresin, and the like.

Examples of such organic solvent include, for instance,nitrogen-containing polar solvents such as N-methyl-2-pyrrolidon(abbreviated as NMP, hereinafter), dimethylformamide dimethylacetamide,1,3-dimethylimidazolyzinon, hexamethyl phosphorasamide and piperazions,sulfoxide-sulfone based sovents such as dimethylsulfoxide,dimethylsulfone and sulfolane, ketone based solvents such as acetone,methylethylketone, diethylketone and acetophenone, ether based solventssuch as dimethylether, dipropylether, dioxane and tetrahydrofuran,halogen based solvent such as chloroform, methylenechloride,trichloroethylene, dichlorothylene, perchloroethane and chlorobenzen,alcohol-phenol based solvents such as methanol, ethanol, propanol,butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol,polyethylene glycol and polypropylene glycol, and aromatichydrocarbon-based solvents such as benzene, toluene and xylene can becited. Among these organic solvents, especially, NMP, acetone,dimethylformamide and chloroform is preferably used. Besides, of theseorganic solvents, either one kind or two or more kinds of mixed solventsare used.

As a method for washing PPS resin with organic solvent, there is amethod of immersing PPS resin in an organic solvent and the like, and itis preferable to be executed while stirring or heating, in order to makethe effect of the present invention more remarkable. The amount oforganic solvent to be used for the PPS resin is not specificallylimited, however the amount is preferably 1 to 100 kg with respect to 1kg of dry PPS resin, more preferably 2 to 50 kg, and still morepreferably 3 to 15 kg.

The washing temperature for washing PPS resin with organic solvent isnot specifically limited and can be optionally selected within a rangefrom normal temperature to around 300° C. Nevertheless, it is preferableto wash at a high temperature of 100 to 300° C., because the washingeffect tends to increase as the washing temperature increases. It isalso possible to wash in a pressure vessel under pressure at atemperature of boiling point of the organic solvent or higher,preferably 250 to 300° C. Besides, the washing time also is notspecifically limited, however, it is preferable to wash for 30 to 60 minor longer, in case of batch type washing. The washing may also becontinuous.

In the present invention, washing of the PPS resin with the organicsolvent may be executed in combination with water washing, in order tomake the aforementioned effect of present invention further remarkable.Besides, in case of using a high boiling point water-soluble organicsolvent such as N-methyl pyrrolidone for organic solvent washing,residual organic solvent can be removed relatively easily by washingwith water after the organic solvent washing. Water used for waterwashing is preferably distilled water and deionized water. The waterwashing temperature is preferably 50 to 90° C., and more preferably, 60to 80° C.

Besides, among the aforementioned post-treatments of PPS resin, the acidtreatment is effective for removing impurities that cause oxidationcoloring, namely chloroform extracts, or improving mechanicalcharacteristics. However, an excessive acid treatment develops aterminal substituents reaction of PPS resin, increases thecrystallization temperature on cooling, resulting in a deterioration oflaser weldability.

Acids used for acid treatment of PPS resin are not specifically limited,provided that they don't have any function to decompose the PPS resin,preferably pH of those acids are 3.5 to 5.5. For instance, acetic acid,silicate, carbonic acid, propyl acid are preferable, and acetic acid isespecially preferable among others. For instance, when the PPS resin isacid treated with a strong acid of pH 2 or lower such as hydrochloricacid, sulfuric acid or phosphoric acid, an excessive acid treatment isprovoked to increase the crystallization temperature on cooling and thelaser weldability could deteriorate. Also, those that decompose anddeteriorate PPS resin, such as sulfuric acid are not preferable.

As for methods of PPS resin acid treatment, there is a method ofimmersing PPS resin in an acid or in an aqueous solution of acid, and itis preferable to stir or heat, in order to make the effect of thepresent invention more remarkable. The treatment time may be 30 to 60min or longer. Further, the amount of acid to be used is preferably 2 to100 kg to 1 kg of dry PPS resin, more preferably 4 to 50 kg, and stillmore preferably 5 to 15 kg. The treatment temperature is notspecifically limitted, it can be treated at a room temperature. In caseof heating, it can be executed at 50 to 90° C. For instance, in case ofusing acetic acid, it is preferable to immerse PPS resin powder in anaqueous solution of PH 4 kept at the room temperature, and to stir for30 to 60 min.

The PPS resin treated by an acid may be washed several times with waterto physically remove residual acid or salts. The water washingtemperature is preferably 50 to 90° C., and more preferably 60 to 80° C.Water used for washing may preferably be distilled water and deionizedwater, in order not to deteriorate the effect of chemical modificationof PPS resin by acid treatment.

The acid treatment of PPS resin may be repeated several times and mayalso be executed in combination with the aforementioned othertreatments.

Besides, among post-treatment of PPS resin, carboxilic metal saltaqueous solution treatment is effective for balancing the laser weldingeffect and mechanical properties improvement of the present invention.

Concrete examples of metal carboxylate used for the carboxilic metalsalt aqueous solution treatment include, for instance, lithium acetate,sodium acetate, potassium acetate, calcium acetate, magnesium acetate,lithium propinate, sodium propinate, potassium propinate, calciumpropinate, magnesium propinate, lithium 2-methylpropinate, rubidiumbutyrate, lithium valerate, sodium valerate, potassium valerate, calciumvalerate, magnesium valerate, cesium hexanoate, lithium heptanoate,lithium 2-methyloctanate, potassium dodecanoate, rubidium4-ethyltetradecanoate, sodium octadecanoate, sodium heneicosanoate,lithium cyclohexane carboxylate, calcium cyclohexane carboxylate,magnesium cyclohexane carboxylate, cesium cyclohexane carboxylate,cesium 3-methylcyclopentane carboxylate, potassium cyclohexylacetate,calcium cyclohexylacetate, magnesium cyclohexylacetate, potassiumbenzoate, calcium benzoate, magnesium benzoate, potassium m-toluate,lithium phenylacetate, calcium phenylacetate, magnesium phenylacetate,sodium 4-phenylcyclohexane carboxylate, calcium 4-phenylcyclohexanecarboxylate, magnesium 4-phenylcyclohexane carboxylate, potassiump-tolylacetate, calcium p-tolylacetate, magnesium p-tolylacetate,lithium 4-ethylcyclohexyl-acetate, calcium 4-ethylcyclohexylacetate,magnesium 4-ethylcyclohexylacetate, other similar salts, and mixturesthereof may be cited. Among others, sodium acetate, calcium acetate andmagnesium acetate are preferable.

It is advantageous to stir or heat during the treatment, in order toobtain a more remarkable effect of carboxilic metal salt aqueoussolution treatment of PPS resin. The treatment time is preferably 30 to60 min or longer. As for the concentration of carboxilic metal saltaqueous solution, it is advantageous to adjust the concentration orquantity of the aqueous solution so that metal carboxylate is 0.1 to 100g to 1 kg of PPS resin. Normally, the treatment temperature ispreferably in the range from a room temperature to 300° C. The PPS resintreated by the carboxilic metal aqueous solution is preferably washedseveral times with water, in order to physically remove salts or thelike. The temperature of water washing is preferably 50 to 95° C.

Distilled water or deionized water is preferably used for washing inorder not to deteriorate the effect of chemical modification of PPSresin by the carboxilic metal aqueous solution. Besides, the treatmentwith the carboxilic metal aqueous solution may be repeated several timesand may also be executed in combination with the aforementioned otherpost-treatments.

(2) Glass Fiber

In the present invention, as for glass fiber (B) to be compounded withPPS resin, those of monofilament diameter of 12 μm or higher are used.By compounding this glass fiber (B), the laser transmittance can beenhanced and the laser weldability can be improved. However, even if themonofilament diameter is less than 12 μm, the main object of the presentinvention can be achieved by using glass fibers of 10 μm or larger butless than 12 μm as the glass fiber (B), in case where a PPS resincomposition has a laser transmittance of 15% or higher at a wavelengthof 940 nm and, at further more, has a heat distortion temperature of230° C. or higher under a load of 1.82 MPa, when the PPS resincomposition is molded to be 2 mm-thick.

The monofilament diameter of the glass fiber (B) is preferably thick, inorder to enhance the laser transmittance of the PPS resin composition.To be more specific, except for the case using a glass fiber having amonofilament diameter of less than 12 μm as mentioned above, themonofilament diameter of the glass fiber to be used is 12 μm or larger,preferably 15 μm or larger, and especially preferably 17 μm or higher.The upper limit of the monofilament diameter of glass fiber ispreferably 35 μm or less from a perspective of lowering of propertiessuch as heat distortion temperature and mechanical strength.

As for the material of the glass fiber (B), E glass, H glass, A glass, Cglass, natural quartz glass, synthetic quartz glass or the like can becited, and in particular E glass and H glass are preferable. The kind ofglass fiber is not specifically limited, provided that they are usuallyused for reinforcing resins, and for instance, chopped strand and milledfiber of long fiber type or short fiber type and the like can be used.It should be noted that the monofilament diameter is the value measuredby the test method based on JIS-R3420 5,6. The average particle diameteris the average value obtained by the micro-track method where 0.70 g ofsample is irradiated with laser beam after ethanol is added andultrasonically dispersed for 3 min.

The compounding ratio of glass fiber (B) to PPS resin may be 1 to 100parts by weight with respect to 100 parts by weight of PPS resin,preferably 5 to 100 parts by weight, and more preferably 10 to 70 partsby weight. In case of a glass fiber having a monofilament diameter of 10μm or larger but less than 12 μm also, it can be added by the samecompounding ratio as in the case of the aforementioned glass fiber of 12μm or larger. The compounding amount of glass fiber to obtain a PPSresin composition having specific laser beam transmittance may beproperly adjusted according to the monofilament diameter and othercondition.

(3) Fillers Except for Aforementioned (B) Component

Fillers except for the aforementioned (B) component may be added to thePPS resin composition of the present invention in order to improve theheat resistance, warpage properties of the molded product, mechanicalstrength and the like, on the condition that the effect of laserweldability, which is the main purpose of the invention, is notdeteriorated.

As concrete examples of fillers except for the aforementioned (B)component may include fibrous fillers, and non-fibrous fillers such asplate, scaly, granular, irregular-shape or crashed fillers. For example,metal fibers such as stainless fiber, aluminum fiber, brass fiber,organic fibers such as aromatic polyamide fiber, gypsum fiber, ceramicfiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber,titanium oxide fiber, silicon carbide fiber, rock wool, alumina hydrate(whisker, plate shape), potassium titanate whisker, barium titanatewhisker, aluminum borate whisker, silicon nitride whisker, talc, kaolin,silica (crushed, spherical), quartz, calcium carbonate, glass bead,glass flake, crushed/irregular-shape glass, glass microballoon, clay,molybdenum disulfide, wollastonite, metal oxides such as aluminumoxide(crushed), translucent alumina (fibrous, plate, scaly, granular,irregular-shape, crushed product), titan oxide(crushed), zinc oxide(fibrous, plate, scaly, granular, irregular-shape, crushed product),metal hydrates such as aluminum hydroxide (fibrous, plate, scaly,granular, irregular-shape, crushed product), aluminum nitride,translucent aluminum nitride(fibrous, plate, scaly, granular,irregular-shape, crushed product), calcium polyphosphate, graphite,metal powder, metal flake, metallic ribbon, and other metal oxides.

Concrete examples of metal elements for metal powder, metal flake andmetallic ribbon are silver, nickel, copper, zinc, aluminum, stainless,iron, brass, chromium, tin and the like. Moreover, though fillers suchas carbon powder, graphite, carbon flake, scaly carbon, carbon nanotube,PAN-based or pitch-based carbon fiber and mica lower the laserweldability, they may be added by such a small amount that does notdeteriorate the practical laser weldability performance, for the purposeof coloring the PPS resin composition of the present invention.

As for fillers except for aforementioned (B) component, E glass, Hglass, A glass, C glass, natural quartz glass, synthetic quartz glass orthe like of plate, scaly, granular, irregular-shape, crushed or otherform may be added.

Among fillers except for the aforementioned (B) component, fillers (C)having a refractive index of 1.6 to 1.8 in (hereinafter sometimesreferred to as “filler (C)”) or fillers (D) having a refractive index ofless than 1.6 or more than 1.8 and a average particle diameter of 30 μmor larger (hereinafter sometimes referred to as “filler (D)”) arepreferable. As filler (C), fibrous or plate aluminum hydrate (forexample, such as gamma-alumina or the like) or fibrous or granular Hglass having a fiber diameter not corresponding to the fiber diameterprescribed for the aforementioned (B) component.

As filler (D), in particular, glass flake and glass bead are preferable.Besides, the size of filler (D) is preferably 50 μm or larger, and morepreferably 80 μm or larger. The upper limit of the size shall preferablybe 1000 μm or less, in order to avoid gate clogging during the injectionmolding.

It should be noted that the refractive index is measured based on amethod according to the total reflection critical angle by a Pulfrichrefractometer, using a cubic test piece of a same composition of 10 mmsquare. The monofilament diameter is the value measured by the testmethod based on JIS-R3420 5,6. The average particle diameter is theaverage obtained by the micro track method where 0.70 g of sample isirradiated with laser beam after ethanol is added and ultrasonicallydispersed for 3 min.

Besides, fillers except for the aforementioned glass fibers may be usedin combination selecting two or more kinds thereof. As such combinationof two or more kinds, for example, combination of fibrous gamma-aluminaand glass bead, or fibrous H glass having a fiber diameter notcorresponding to that of the aforementioned (B) component and glassflake, combination of plate gamma-alumina and granular H glass,combination of glass flake and glass bead and the like can be cited.

Fillers mentioned above may be used by treating the surface thereof witha well-known coupling agent (for example, silane-based coupling agents,titanate-based coupling agents) or other surface treatment agents.

The total compounding amount of filler (C) and/or filler (D) withrespect to 100 parts by weight of PPS resin (A) may be 1 to 200 parts byweight, preferably 5 to 100 parts by weight, and more preferably 10 to70 parts by weight, from a perspective of laser weldability, heatresistance, mechanical strength and the like. If the compounding amountof filler (C) and/or filler (D) is less than 1 part by weight, theimprovement effect of heat resistance, mechanical strength and lowwarpage properties are not evident. On the contrary, if it is more than200 parts by weight, it is not practical because the mechanical strengthand fluidity deteriorate.

It should be noted that the total compounding amount of filler (C)and/or filler (D) for obtaining a PPS resin composition having aspecific laser beam transmittance may be properly adjusted according tothe kind of filler (C) and/or filler (D) and other conditions, inaddition to the kind, monofilament diameter and compounding amount ofthe glass fiber (B).

(4) Amorphous Resin

Amorphous resin (E) may be added to the PPS resin composition of thepresent invention for the purpose of improvement of laser weldabilityand low warpage.

As examples of amorphous resin (E), for instance, cycloolefin polymer,cycloolefin copolymer, polycarbonate, polyphenylene ether, polysulfone,polyethersulfone, polyarylate, polyetherimide, polyamideimide and thelike can be cited. Among them, polyamideimide, polyarylate,polyethersulfone, polyetherimide, polysulfone, polyphenylether arepreferable from a perspective of heat resistance and compatibility, andparticularly preferable are polyamideimide, polyarylate,polyethersulfone, polyetherimide, polysulfone. Especially,polyamideimide (E1), polyetherimide (E2), polyethersulfone (E3) andpolysulfone (E4) permit to obtain a significantly excellent lasertransmittance, when finely dispersed in the PPS resin.

The compounding amount of amorphous resin (E) with respect to 100 partsby weight of PPS resin (A) is 0.1 to 200 parts by weight, preferably 1to 150 parts by weight, and more preferably 1 to 70 parts by weight. Itis possible to improve laser weldability, low warpage properties, heatresistance and mechanical strength and the like of the PPS resincomposition in good balance by adopting such compounding amounts. If thecompounding amount of amorphous resin (E) is less than 0.1 part byweight, the improvement effect of laser weldability and low warpageproperties or the like can not be obtained, and, if more than 200 partsby weight, the heat resistance, mechanical strength and fluidity of thePPS resin composition deteriorate.

Besides, two or more kinds of the aforementioned amorphous resin (E) canbe used in combination in order to balance the laser transmittance ofthe PPS resin composition and warpage properties of the molded product.The compounding amount of amorphous resin (E) for obtaining a PPS resincomposition having a specific laser beam transmittance may be properlyadjusted according to the kind of amorphous resin and other conditions.

(5) Silane Compound

A silane compound (F) may be added to the PPS resin composition of thepresent invention for the purpose of improvement of laser weldabilityeffect and mechanical strength and the like.

As silane compound (F), for instance, in addition to epoxysilanecompounds, aminosilane compounds, ureidesilane compounds,isocyanatesilane compounds, various other kinds may be used. Besides,concrete examples of such silane compound (F) include, for instance,epoxy group containing alcoxysilane compounds such asgamma-glycidoxypropyl-trimethoxysilane,gamma-glycidoxypropyltriethoxysilane,beta-(3,4-epoxycyclohexyl)ethyltri-methoxysilane, mercapto groupcontaining alcoxysilane compounds such as gamma-mercapto-propyltriemethoxysilane, gamma-mercaptopropyl triethoxysilane, ureido groupcontaining alcoxysilane compounds such as gamma-ureidopropyltriethoxysilane, gamma-ureidoxypropyl triemethoxysilane,gamma-(2-ureidoethyl)aminopropyl trimethoxy-silane, isocianate groupcontaining alcoxysilane compounds such as gamma-isocianatopropyltriethoxysilane, gamma-isocianatopropyl trimethoxysilane,gamma-isocianatopropyl methyldimethoxysilane, gamma-isocianatopropylmethyldiethoxysilane, gamma-isocianato-propyl etyldimethoxysilane,gamma-isocianatopropy ethyldiethoxysilane, gamma-isocianato-propyltrichlorosilane, amino group containing alcoxysilane compounds such asgamma-(2-aminoethyl) aminopropyl methyldimethoxysilane,gamma-(2-aminoethyl) aminopropyl trimethoxysilane, gamma-amino-propyltrimethoxy-silane, and hydroxy group containing alcoxysilane compoundssuch as gamma-hydroxypropyl trimethoxysilane, gamma-hydroxy-propyltriethoxysilane and the like.

The compounding amount of silane compound (F) with respect to 100 partsby weight of PPS resin (A) is 0.01 to 3 parts by weight, preferably 0.05to 2 parts by weight, and more preferably 0.1 to 1 parts by weight. Itis possible to improve laser weldability effect and mechanical strengthin good balance by adding such silane compound. If the compoundingamount of silane compound (F) is far less than 0.01 part by weight, theeffect of the present invention can not be obtained, and, if more than 3parts by weight, it causes a deterioration of fluidity and an increaseof gas during the injection molding. Two or more kinds of theaforementioned silane compounds may be used in combination.

(6) Antioxidant

Antioxidant (G) may be added to the PPS resin composition of the presentinvention. The addition of this antioxidant (G) permits to prevent thelaser transmittance from lowering by the oxidation coloring.

Examples of such antioxidant (G) includes for example, calciumhypophosphite, phenolic compounds such as 2,6-di-t-butyl-4-methylphenol,tetrakis (methylene-3-(3,5-di-t-butyl-4-hydroxyphenil)propionate)methane, tris (3,5-di-t-butyl-4-hydroxybenzine) isocyanurate,sulfur compounds such as dilauryl-3,3′-thiodipropyonate,dimyristyl-3,3′-thiodipropinate, phosphorous compouns such astrisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, andamong others, calcium hypophosphite is preferable.

The compounding amount of antioxidant (G) with respect to 100 parts byweight of PPS resin (A) may be 0.01 to 3 parts by weight, preferably0.05 to 2 parts by weight, and more preferably 0.1 to 1 parts by weight.In addition, two or more kinds of antioxidant may be used incombination.

(7) Elastomer

Elastomer (H) can be added to the PPS resin compositions of the presentinvention. This addition of elastomer (H) improves the shock impactresistance and the cold and heat resistance of the PPS resincompositions.

Examples of the elastomer (H) are olefinic elastomer, modified olefinicelastomer, styrene elastomer and so on. Among them, olefinic elastomersinclude: polymers or copolymers obtained by polymerization of a kind ormore kinds of ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, isobutylene or the like; and copolymers ofalpha-olefin, alpha, beta-unsaturated carbonic acid such as methylacrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methylmetharcylate, ethyl methacrylate and butyl methacrylate, and alkyl esterthereof. Concrete examples of olefinic elastomers are polyethylene,polypropylene, ethylene/propylene copolymer (hereinafter, “/” denotesco-polymerization), ethylene/butene-1 copolymer, ethylene/methylacrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butylacrylate copolymer, ethylene/methyl methacrylate copolymer,ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylatecopolymer, and so on.

Modified olefinic elastomers are obtained by introducing monomercomponent having functional group such as epoxy group, acid anhydridegroup and ionomer (hereinafter, referred to as functionalgroup-containing component) into the aforementioned olefinic elastomers.This functional group containing component include: monomers containingacid anhydride group such as maleic anhydride, itaconic anhydride,citraconic anhydride, endobicyclo[2.2.1]5-heptene-2,3-dicarboxylic acid,endobicyclo[2.2.1]5-heptene-2,3-dicarboxylic anhydride; monomerscontaining epoxy group such as glycidyl acrylate, glycidyl methacrylate,glycidil ethacrylate, glycidyl itaconate, glycidyl citraconate; andmonomers containing ionomers such as metal complex carboxylate.

Methods for introducing these functional group containing component arenot especially limited and they include: copolymerization when olefinic(co)polymer similar to those used as the aforementioned olefinicelastomer is (co)polymerized; and graft-introduction to olefinic polymerusing a radical initiator. It is proper that amount of introducedfunctional group containing component is within the range of 0.001 to 40mol %, preferably 0.01 to 35 mol % to the entire olefin (co) polymer.

Olefin (co)polymers obtained by introducing monomer component having afunctional group such as epoxy group, acidic anhydride group and ionomerinto especially useful olefin polymers include:ethylene/propylene-g-glycidyl methacrylate copolymer (hereinafter, “g”referred as graft), ethylene/butane-1-g-glycidyl methacrylate copolymer,ethylene glycidyl acrylate copolymer, ethylene/glycidyl methacrylatecopolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer,ethylene/methyl methacrylate/glycidyl methacrylate copolymer,ethylene/propylene-g-maleic anhydride copolymer,ethylene/butane-1-g-maleic anhydride copolymer, ethylene/methylacrylate-g-maleic anhydride copolymer, ethylene/ethyl acrylate-g-maleicanhydride copolymer ethylene/methyl methacrylate-g-maleic anhydridecopolymer, ethylene/ethyl methacrylate-g-maleic acid anhydridecopolymer, zinc complex of ethylene/methacrylate copolymer, magnesiumcomplex of ethylene/methacrylate copolymer and sodium complex ofethylene/methacrylate copolymer.

Preferable examples include, ethylene/glycidyl methacrylate copolymer,ethylene/metyl acrylate/glycidyl methacrylate copolymer, ethylene/metylmethacrylate/glycidyl methacrylate copolymer, ethylene/butene-1-g-maleicanhydride copolymer, ethylene/ethyl acrylate-g-maleic anhydridecopolymer, and so on.

As especially preferable examples, ethylene/glycidyl methacrylatecopolymer, ethylene/metyl acrylate/glycidyl methacrylate copolymer,ethylene/metyl methacrylate/glycidyl methacrylate copolymer, or the likecan be cited.

On the other hand, concrete examples of styrene elastomers includestyrene/butadiene copolymer, styrene/ethylene/butadiene copolymer,styrene/ethylene/propylene copolymer, styrene/isoprene copolymer and soon. Among them, styrene/butadiene copolymer is preferable. Morepreferably, epoxy copolymer of styrene/butadiene can be named.

The compound quantity of elastomer (H) is 0.5 to 20 parts by weightto100 parts by weight of PPS resin (A), preferably 0.8 to 10 parts byweight thereto, and more preferably 1 to 6 parts by weight thereto. Thecompound quantity of elastomer (H) for obtaining PPS resin compositionshaving a specific laser transmittance may be adjusted according to thekind of elastomer and other conditions.

Besides, 2 or more kinds of the aforementioned elastomers can be usedtogether, in order to have shock impact resistance, heat and coldresistance and laser transmittance in a balanced manner.

(8) Other Additives

Other additives can be added to the PPS resin compositions of thepresent invention, within the range not to reduce the advantageouseffects of the invention. Those additives include: thermal stabilizers(hindered phenol family, hydroquinone family, phosphate family,substitutions thereof and so on); weather resistant agent (resorcinolfamily, salicylate family, benzotriazole family, benzophenone family,hindered amine family and so on); mold release agents and lubricants(montan acid, metal salt thereof, ester thereof and half ester thereof,stearyl alcohol, stearamide, various kinds of bisamide, bis-urea,polyethylene wax, and others); pigments (cadmium sulfide,phthalocyanine, carbon black for coloring, and so on), dyes (nigrosineand so on); nucleating agents for crystallization (talc, silica, kaolin,clay, polyether ether ketone, and so on); plasticizers (p-oxy octylbenzoate, N-butyl benzene sulfonamide, and so on); antistatic agents(alkyl sulfate type anionic antistatic agent, quaternary ammonium salttype cationic antistatic agent, nonionic antistatic agent such aspolyoxyethylene sorbitan monostearate, betaine type amphotericantistatic agent, and so on); flame retardants (red phosphorus,phosphate ester, melamine cyanurate, hydroxydes such as magnesiumhydroxide and aluminum hydroxyde, ammonium poplyphosphate, brominatedpolystyrene, brominated polyphenylene ether, brominated polycarbonate,brominated epoxy resin, or combination of these brominated flameretardants and antimony trioxide, or the like); and other polymers.

(9) Compounding of Respective Components

The PPS resin compositions of the present invention can be produced bywell-known methods. In short, they can be prepared by taking theaforementioned PPS resin (A) and glass fiber (B) as main components,selecting filler (C), filler (D), amorphous resin (E), silane compound(F), antioxidant (G) or elastamer (H) as arbitrary additive, and thenmixing the main components and the selected additive beforehand, orwithout pre-mixing, feeding them to an extruder or the like wheremelting as well as kneading them sufficiently. Besides, it is preferablethat glass fiber (B), fibrous/flaky filler (C) and fibrous/flaky filler(D) are supplied using the side feeder of an extruder in order toprevent fibrous/flaky breakage during melting/kneading, while PPS resin(A), filler (C) other than fibrous/flaky one, filler (D) other thanfibrous/flaky one, amorphous resin (E), silane compound (F), antioxidant(G) and elastamer (H) are supplied through the main supply inlet of theextruder.

Besides, concerning equipments for producing PPS resin compositions, itcan be produced by using, for instance, a single shaft extruder, doubleshaft extruder, triple shaft extruder provided with “Unimelt” (R) typescrew(s) and a kneader type kneader, melting and kneading at 180 to 350C.°.

(10) PPS Resin Compositions

It is essential for the PPS resin compositions of the present inventionthat the crystallization temperature during cooling is 205 C.° or less,more preferably, 200 C.° or less. Laser weldability can further beimproved by lowering the crystallization temperature during cooling. Thelower limit of crystallization temperature during cooling is notespecially limited; however, it is preferable to set 170 C.° as thelower limit, since excessive low temperature decreases the heatresistance.

In addition, for the PPS resin compositions of the present invention, itis preferable that the chloroform-extractable content is 0.5 weight % orlower. This can improve the laser weldability furthermore. Still morepreferably, the chloroform-extractable content is 0.3 weight % or less.The lower limit of the chloroform-extractable content is not especiallylimited, but should be within a range not to ruin the effect of laserweldability of the present invention, heat resistance, mechanicalstrength, and so on.

When the PPS resin compositions of the present invention is molded into2 mm thick, the transmittance for laser beam having a wavelength of the940 nm of the molded product is preferably 15% or higher, morepreferably 17% or higher and especially preferably 20% or higher. Also,the heat distortion temperature of the molded product under a load of1.82 MPa is preferably 230 C.° or higher, more preferably 240° or higherand especially preferably 260 C.° or higher.

The crystallization temperature during cooling, chloroform-extractablecontent, laser transmittance and heat distortion temperature of the PPSresin compositions used for the present invention are based on thefollowing measuring method.

The crystallization temperature during cooling is the temperatureresulting from the PPS resin, obtained by sampling about 10 mg from amolded product, pellet, or crushed PPS resin compositions, heating it atthe heating rate of 20 C.°/min, retaining at 340 C.° for 5 min, coolingit at the rate of 20 C.°/min and then measuring the crystallization peak(exothermic peak) temperature, using a differential scanning calorimeter(DSC-7 made by Perkin Elmer).

For the chloroform-extractable content, pellets of PPS resincompositions are frozen and crushed, then this crushed sample isclassified with 32 to 60 mesh, washed five times with 30 ml of methanolto remove deposits, vacuum dried and after these processes 2 g of sampleis measured. The sample of 2 g is wholly extracted under reflux with 20g of chloroform at 85 C.° for 5 hours (Soxhlet extraction), using aSoxhlet extractor. Chloroform is collected and vacuum dried at 23 C.°for 1 hour. The measurement is performed by dividing the dry weight bythe pre-extraction weight.

As for the laser transmittance, a test piece of 80 mm×80 mm×2 mm moldedusing an injection molding machine UH100 (made by Nissei PlascicIndustrial Co., Ltd.) is used. The molding conditions thereof are 320C.° cylinder temperature and the mold temperature of 130 C.°. Anultraviolet near infrared spectrophotometer (UV-3100) made by ShimadzuCorp. is used as test machine and an integrating sphere as detector. Thelaser transmittance is beam transmittance indicating in percentage theratio of transmitted beam quantity to incident beam quantity when alaser beam of near infrared 940 nm wavelength transmits through a testpiece of 2 mm thick.

The heat distortion temperature is the one of a comuted test piece of 7mm W×6.5 mm H×126 mm L, injection molded at 320 C.° of cylindertemperature and 130 C.° of mold temperature, using the injection moldingmachine UH100 (made by Nissei Plastic Industrial Co., Ltd.) which aremeasured according to ASTM-D648, under 1.82 MPa load.

(11) Molding and Applications of PPS Resin Composition

For the PPS resin composition of the present invention, any ofwell-known molding methods of thermoplastic resin, such as injectionmolding, extrusion molding, compression molding, blow-molding,injection-compression molding, transfer molding, vacuum molding can beused. Among them, injection molding is especially preferable.

The obtained molded product, having an excellent laser weldability, canhave an excellent performance as the molded product at the laser beamtransmission side when the composite molded product is obtained bybonding 2 or more resin molded products in the laser welding method.Resin for the other side is not especially defined and it may be PPSresin, or resins other than PPS resin.

The applications of the composite molded product include, for instance,electrical and electronic application, automobile application, generalmiscellaneous goods application, construction material, and so on. To bemore specific, it is useful for electronic component case of personalcomputer, liquid crystal projector, mobile equipment, cellular phone orthe like, modules of switch or the like, parts for bonding in a remotecontroller, module products of electric equipment parts, module parts inengine room, throttle cover parts, intake manifold, underhood parts,radiator parts, cockpit module parts used for instrument panel or hollowcontainer, covering box, parts of installed antenna requiringelectromagnetic wave shield property in the other information andcommunication fields, or applications requiring a high dimensionalaccuracy for construction members, automobile parts application wherethe substitution of metals is desired for weight saving or the like,molded product used by laser welding for electrical and electroniccomponent application, and so on. As the composite molded product has anexcellent weld strength, on laser welding bonding resin molded productfor various application, it is especially useful for the molded productat the laser beam transmission side.

The PPS resin composition of the present invention, having an excellentlaser transmissive property, permits to obtain a satisfactory bondingforce, even if the thickness of the transmission part of its weldingsite in which laser beam transmits is in the relatively thick range of 5mm or less. Among others, a stronger bonding force can be obtained if 3mm or less, especially 2 mm or less and further 1.5 mm or less. Itshould be noted that it is preferable the lower limit thickness is 0.1mm, especially 1 mm, in order to obtain practical molded productstrength and productivity, or in order to obtain such a degree offreedom of composition design that permits to add another function byadding an additive to the composition.

In case of obtaining the molded product of PPS resin composition of thepresent invention by injection molding, it is possible to lower the moldtemperature. By lowering the mold temperature, the transmittance forlaser beam of the PPS resin composition molded product can be improved.The mold temperature is preferably 100° C. or lower and more preferably,it can be set to 80° C. or lower. It should be noted that the lowerlimit of the mold temperature is preferably 40° C., because the moldingin a low-temperature mold accompanies the loss of flowability of resinand the defective appearance of the molded product, and so on.

The other resin molded product is not especially limited when laserwelding a composite molded product using a molded product of PPS resincomposition of the present invention as the molded product at the laserbeam absorption side; however, preferably, it contains PPS resin. Also,it is preferable that the composite molded product obtained by laserwelding the molded product of PPS resin composition of the presentinvention is heat-treated after laser welding. This heat-treatingpermits to improve the dimensional stability, mechanical strength or thelike after the laser welding. It is especially effective in case wherethe molded product at the laser beam transmission side is obtained atthe mold temperature of 100° C. or lower.

EXAMPLES OF EMBODIMENT

The present invention shall be described more particularly by means ofembodiments and comparative examples. These are illustrated only asexamples, and the present invention is not limited to the above.

PPS resin, glass fiber and other compounding components used for theembodiments and comparative examples described below are selected fromthe following groups of material (1) to (7).

(1) PPS Resin

a. PPS-1:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol), sodium acetate 0.787 kg(9.6 mol) and NMP 5 kg are thrown in an autoclave with agitator, heatedgradually to 205° C. introducing nitrogen, and water of 3.6 litter isdistillated. Next, the reaction vessel is cooled to 180° C., and1,4-dichlorobenzen 3.712 kg (25.25 mol) and NMP 2.4 kg are added, sealedunder nitrogen, heated to 270° C., and thereafter, let react at 270° C.for 2.5 hours. Next, the above is thrown in NMP 10 kg that is heated to100° C., agitated continuously for about one hour and filtered, andwashed three times for 30 minutes with hot water of 80° C. This isfiltered, thrown in 25 litter of aqueous solution containing calciumacetate 10.4 g, agitated continuously for about one hour at 192° C. in asealed autoclave, filtered, washed with ion exchange water of about 90°C. until the filtrate pH becomes 7, and dried for 24 hours at 80° C.under reduced pressure, to obtain PPS-1 of 180° C. in crystallizationtemperature during cooling, 0.30 weight % in chloroform-extractablecontent, and 100 g/10 minutes in MFR.

It should be noted that MFR is measured under a load of 5 kg (based onJIS-K7210), after having dried 5 g of PPS resin powder at 130° C. forthree hours and retained at 315.5° C. for 5 minutes.

b. PPS-2:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol), sodium acetate 0.656 kg (8mol) and NMP 5 kg are thrown in an autoclave with agitator, heatedgradually to 205° C. introducing nitrogen, and water of 3.6 litter isdistillated. Next, the reaction vessel is cooled to 180° C.,1,4-dichlorobenzen 3.712 kg (25.25 mol) and NMP 2.4 kg are added, sealedunder nitrogen, heated to 270° C., and thereafter, let react at 270° C.for 2.5 hours. Next, the above is thrown in NMP 10 kg that is heated to100° C., agitated continuously for about one hour and filtered, andwashed three times for 30 minutes with hot water of 80° C. This isfiltered, thrown in 25 litter of aqueous solution containing calciumacetate 10.4 g, agitated continuously for about one hour at 192° C. in asealed autoclave, filtered, washed with ion exchange water of about 90°C. until the filtrate pH becomes 7, and dried for 24 hours at 80° C.under reduced pressure, to obtain PPS-2 of 185° C. in crystallizationtemperature during cooling, 0.4 weight % in chloroform-extractablecontent and 60 g/10 minutes in MFR.

c. PPS-3:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol), sodium acetate 0.761 kg(9.28 mol) and NMP 5 kg are thrown in an autoclave with agitator, heatedgradually to 205° C. introducing nitrogen, and water of 3.6 litter isdistillated. Next, the reaction vessel is cooled to 180° C.,1,4-dichlorobenzen 3.712 kg (25.25 mol), 1,3,5-trichlorobenzen 3.27 kg(0.018 mol) and NMP 2.4 kg are added, sealed under nitrogen, heated to270° C., and thereafter, let react at 270° C. for 2.5 hours. Next, theabove is thrown in NMP 10 kg that is heated to 100° C., agitatedcontinuously for about one hour and filtered, and washed three times for30 minutes with hot water of 80° C. This is filtered, thrown in 25litter of aqueous solution containing calcium acetate 10.4 g, agitatedcontinuously for about one hour at 192° C. in a sealed autoclave,filtered, washed with ion exchange water of about 90° C. until thefiltrate pH becomes 7, and dried for 24 hours at 80° C. under reducedpressure, to obtain PPS-3 of 180° C. in crystallization temperatureduring cooling, 0.4 weight % in chloroform-extractable content and 70g/10 minutes in MFR.

c. PPS-4:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol), sodium acetate 0.69 kg(98.25 mol) and NMP 4.1 kg are thrown in an autoclave with agitator,heated gradually to 205° C. introducing nitrogen, and water of 3.6litter is distillated. Next, the reaction vessel is cooled to 180° C.,p-dichlorobenzen 3.582 kg (24.4 mol), m-dichlorobenzen 0.188 kg (1.28mol) and NMP 3.2 kg are added, sealed under nitrogen, heated to 270° C.,and thereafter, let react at 270° C. for 2.5 hours. Next, the above isthrown in NMP 10 kg that is heated to 100° C., agitated continuously forabout one hour and filtered, and washed three times for 30 minutes withhot water of 80° C. This is filtered, dried for 24 hours at 80° underreduced pressure, to obtain PPS-4 of 5 mol % in m-phenylene sulfide unitto the total of m-phenylene sulfide and p-phenylene sulfide, 180° incrystallization temperature during cooling, 0.5 weight % inchloroform-extractable content and 160 g/10 minutes in MFR.

d. PPS-5:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol), sodium acetate 0.656 kg (8mol) and NMP 5 kg are thrown in an autoclave with agitator, heatedgradually to 205° C. introducing nitrogen, and water of 3.6 litter isdistillated. Next, the reaction vessel is cooled to 180° C.,1,4-dichlorobenzen 3.756 kg (25.55 mol) and NMP 2.4 kg are added, sealedunder nitrogen, heated to 270°, and thereafter, let react at 270° C. for2.5 hours. Next, the above is thrown in NMP 10 kg that is heated to 100°C., agitated continuously for about one hour and filtered, and washedthree times for 30 minutes with hot water of 80° C. This is thrown in 25litter of acetic acid aqueous solution of pH 4 that is heated to 90°,agitated continuously for about one hour, washed with ion exchange waterof about 90° C. until the filtrate pH becomes 7, and dried for 24 hoursat 80° C. under reduced pressure, to obtain PPS-5 of 215° C. incrystallization temperature during cooling, 0.5 weight % inchloroform-extractable content and 300 g/10 minutes in MFR.

e. PPS-6:

Sodium sulfide 9 hydrobase 6.005 kg (25 mol) and NMP 5 kg are thrown inan autoclave with agitator, heated gradually to 205° C. introducingnitrogen, and water of 3.6 litter is distillated. Next, the reactionvessel is cooled to 180° C., 1,4-dichlorobenzen 3.763 kg (25.6 mol) andNMP 1.8 kg are added, sealed under nitrogen, heated to 274° C., and letreact at 274° C. for 0.8 hours. A drain valve installed in the lowerpart of the autoclave is opened at room temperature and normal pressureto extract the contents, which are washed with hot water of 80° C. Thisis filtered, thrown in 25 litter of aqueous solution containing calciumacetate 10.4 g, agitated continuously for about one hour at 192° C. in asealed autoclave, filtered, washed with ion exchange water of about 90°C. until the filtrate pH becomes 7, and the polymer is dried at 120° C.for 8 hours, heated thereafter at 215° C., to obtain PPS-6 of 215° C. incrystallization temperature during cooling, 2.5 weight % inchloroform-extractable content and 300 g/10 minutes in MFR.

f. PPS-7:

PPS resin M3910 made by TORAY (210° C. in crystallization temperatureduring cooling, 3.0 weight % in chloroform-extractable content, and 3000g/10 minutes in MFR)

(2) Glass Fiber

a. Glass fiber (GF1):

T-747 H (Nippon Electric Glass) E glass, monofilament diameter 10.5 μm,refractive index (n_(D)) 1.55

b. Glass fiber (GF2):

T-747 (Nippon Electric Glass) E glass, monofilament diameter 13 μm,refractive index (n_(D)) 1.55

c. Glass fiber (GF3):

T-747 N (Nippon Electric Glass) E glass, monofilament diameter 17 μm,refractive index (n_(D)) 1.55

d. Glass fiber (GF4):

T-747 T (Nippon Electric Glass) E glass, monofilament diameter 23 μm,refractive index (n_(D)) 1.55

e. Glass fiber (GF5):

T-717 G (Nippon Electric Glass) E glass, monofilament diameter 9.5 μm,refractive index (n_(D)) 1.55

(3) Fillers Other than Glass Fiber

a. Glass flake (GFL):

REFG311 (flaky filler, SNG petrotex) E glass, average particle diameterobtained by micro-track method is 58 μm. Refractive index (n_(D)) 1.55

b. Glass bead (GB1):

EGB731B2 (made by Potters-Ballotini Co.,Ltd.) E glass, average particlediameter: 20 μm (Micro-track method), refractive index (n_(D)) 1.55

c. Glass bead (GB2):

J-54 (made by Potters-Ballotini Co.,Ltd.) A glass, average particlediameter: 300 μm (Micro-track method), refractive index (n_(D)) 1.52

d. E Glass crushed product (EG):

E glass (made by Nippon Electric Glass) is crushed by Henschel mixer,sieved by 63 μm pass, and 9.5 μm undercut to obtain EG with 20 μm inaverage particle diameter (Micro-track method). Refractive index (n_(D))1.55

e. H Glass crushed product (HG1):

H glass (made by Nippon Electric Glass) is crushed by Henschel mixer,sieved by 63 μm pass, and 9.5 μm undercut to obtain HG1 with 20 μm inaverage particle diameter (Micro-track method). Refractive index (n_(D))1.74

f. H Glass crushed product (HG2):

H glass (made by Nippon Electric Glass) is crushed by Henschel mixer,sieved by 355 μm pass, and 45 μm undercut to obtain HG2 with 150 μm inaverage particle diameter (Micro-track method). Refractive index (n_(D))1.74

g. Alumina hydrate (BM1):

“Terracess” BMT33 (made by OTSUKA Chemical Co., Ltd.) γ-alumina· 1hydrate, plate-shape, 5 μm in average particle diameter (Micro-trackmethod), refractive index (n_(D)) 1.66

h. Burned substance of alumina hydrate (BM2):

“Terracess” BMT33-B (made by OTSUKA Chemical Co., Ltd.) γ-alumina,plate-shape, 5 μm in average particle diameter (Micro-track method),refractive index (n_(D)) 1.68

i. Alumina hydrate (BM3):

“Terracess” BMI (made by OTSUKA Chemical Co., Ltd.) γ-alumina 1 hydrate,whisker-shape, 7 μm in average particle diameter (Micro-track method),refractive index (n_(D)) 1.66

It should be noted that 335 μm pass means passage through thecorresponding sieve, and 9.5 μm undercut means failed passage throughthe corresponding sieve.

(4) Amorphous Resin

a. Polyamide-imide (PAI):

It is synthesized by acid chloride low temperature solutionpolymerization method, using N,N-dimethylacetoamide as polymerizationsolvent. The detail thereof is shown below.

12 kg of diamino diphenylether (DDE) and 2.0 kg of methaphenilenediamine (MPDA) are dissolved in 65 litters of N,N-dimethylacetoamide(DMAC), and 15 kg of powder trimellitic anhydride monochloride (TMAC) isadded by such a speed that the inner temperature does not exceed 30° C.by cooling with ice bath. After having added the whole TMAC, 1.7 kg oftrimellitic anhydride (TMA) is added, agitated, and retained at 30° C.for two hours. The viscous polymerization solution is introduced in acutter mixer filled with water of 100 litters and agitated at a highspeed to separate out slurry like polymer. Thus obtained slurry isdehydrated by a centrifugal separator. Dehydrated cake is washed withwater of 20 litters at 60° C., and dehydrated again with the centrifugalseparator. Thus obtained cake is dried at 220° C. for five hours using ahot air drier, to obtain powder polymer of glass transition temperature(Tg)=275° C.

b. Polyetherimide (PEI)

“ULTEM” 1010 (made by GE Plastics Japan), glass transition temperature(Tg)=215° C.

c. Polyether sulfone (PES):

“SUMIKAEXCEL” 3600P (made by Sumitomo Chemical Co., Ltd.), glasstransition temperature (Tg)=220° C.

d. Polysulfone (PSU):

“UDEL” P-1700 (made by Amoco Engineering Polymers Co., Ltd.), glasstransition temperature (Tg)=190° C.

e. Polyarylate (PAR):

“U-polymer” U-100 (made by Unitika), glass transition temperature(Tg)=195° C.

It should be noted that the glass transition temperature is obtained atthe heating rate of 20°/minute using a differential scanning calorimeter(DSC-7: made by Parkin Elmer).

(5) Silane Compound

a. Silane compound:

“KBM303” (made by Shinetsu Chemical Co., Ltd.) β-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane

(6) Antioxidant

a. Antioxidant:

“Calcium hypophosphite” (made by Taihei Chemical Industry Co., Ltd.)

(7) Elastomer

a. Elastomer-1 (ER-1):

“BF-E” (Sumitomo Chemical Industry Co., Ltd.) ethylene/glycidylmethacrylate=97.6/2.4 (mol %) copolymer.

b. Elastomer-2 (ER-2):

“Tafmer A4085” (Mitsui Chemicals) ethylene/butene-1=90.8/9.2 (mol %)copolymer

Also, performances of PPS resin composition obtained by embodiments andcomparative examples explained below are evaluated by the measurementmethod described in the following (1) to (4).

(1) Warpage Property

A square plate of 80 mm×80 mm×1 mm thickness is manufactured by using aninjection molding machine UH1000 (Nissei Resin Industry Co., Ltd.). Themolding condition is 320° C. for cylinder temperature (resin temperature310° C. for the example described in Table 5) and 130° C. for the moldtemperature. The warpage property, when it is heat-treated at 130° C.for one hour, is evaluated.

For the evaluation, one of four sides of the square plate is pressed,and the warping is evaluated as A if less than 0.8 mm, B if less than 1mm, C if less than 1 mm, D if less than 3 mm, and E if 3 mm or more.

(2) Laser Weld Strength Evaluation

A laser transmissive property evaluation test piece of 80 mm×80 mm×2.0mm thickness is manufactured by using an injection molding machineUH1000 (Nissei Resin Industry Co., Ltd.). The molding condition is 320°C. for cylinder temperature and 130° C. for the mold temperature.Furthermore, the test piece is worked into 24 mm×70 mm×2.0 mm, 24 mm×70mm×2.5 mm, 24 mm×70 mm×3.5 mm, 24 mm×70 mm×4.5 mm, and 24 mm×70 mm×5.0mm respectively, according to the evaluation thickness 2.0 mm, 2.5 mm,3.5 mm, 4.5 mm, and 5.0 mm, the sample for transmission and the sampleat the absorption side are superposed for setting the length L to 30 mm,the laser weld distance Y is set to 20 mm, and the laser welding isperformed, to measure the tensile break strength.

It should be noted that the welding conditions and the weld strengthmeasurement conditions are as follows.

The laser welding is performed with conditions permitting to obtain thebest weld strength within a range of 15 to 35 W for output and within arange of 1 to 50 mm/sec for laser scanning speed, using MODULASC made byLeister. It should be noted that the focal length is fixed at 38 mm andthe focal diameter is fixed at 0.6 mm. In addition, a general tensiletester (AG-500B) is used for measuring the weld strength, both ends ofthe test piece are fixed, and the tensile test is executed so thattensile shearing stress generates in the welding site. The tensile speedis 1 mm/minute and the span is 40 mm for measuring the strength. Theweld strength is taken as the stress when the welding site is broken. Itshould be noted that thermoplastic resin composition of the presentinvention is used for the laser transmission sample, and material where0.4 parts of carbon black is added further to the sample at thetransmission side respectively is used for the sample at the laserabsorption side.

(3) Cold and Heat Resistance

A cold and heat resistance evaluation test piece is manufactured byfixing a metal piece of 47.0 mm length×47.0 mm width×28.6 mm height inthe mold, and over-molding resin with 1.5 mm thickness around the outerperiphery of the metal piece, using the injection molding machine UH1000(Nissei Resin Industry Co., Ltd.). The molding condition is 320° C.(resin temperature is 310° C. for the example described in Table 5) forcylinder temperature and 130° C. for the mold temperature. THERMAL SHOCKCHANBER TSA-100S-W type (made by TABAY) is used for evaluation, the testpiece is exposed to 130° C. (high temperature side) and −40° C. (lowtemperature side) respectively for one hour as one cycle, the number ofcycles until crack is generated is visually determined, and it isevaluated as A if the average number of cycles when N=3 is 1000 cyclesor more, B if 500 cycles or more, C if 300 cycles or more, D if 30cycles or more, and E if less than 30 cycles.

(4) Heat Resistance

A test piece of 12.7 mm×12.7 mm×3.2 mm thickness is manufactured at theresin temperature of 310° C. and at the mold temperature shown in Table1 by using the injection molding machine UH1000 (Nissei Resin IndustryCo., Ltd.), and the deflection temperature under load is evaluated under0.46 MPa load, according to ASTM D648.

Embodiments 1-30, Comparative Examples 1-7

Respective materials from PPS resin group described in (1), glass fibergroup described in (2), filler group other than glass fiber described in(3), amorphous resin group described in (4), silane compound describedin (5) and antioxidant described in (6) mentioned above are selectedwith the combination and quantity described in Table 1 to 3, compounded,and pelletized respectively by the double shaft extruder PCM with 3 holestrand mold head at the resin temperature of 310° C. to prepare pelletof PPS resin composition. Molded products for respective evaluationtests were prepared from these pellets of PPS resin composition for theevaluation of crystallization temperature during cooling,chloroform-extractable content, laser transmissivity, heat distortiontemperature and, at the same time, laser weld strength and warpageproperty, to obtain results shown in Table 1 to 3.

Embodiments 31-52

As mentioned above, respective materials from PPS resin group describedin (1), glass fiber group described in (2), filler group other thanglass fiber described in (3), amorphous resin group described in (4),silane compound described in (5) and antioxidant described in (6) areselected with the combination and quantity described in Table 4,compounded, and pelletized respectively by the double shaft extruder PCMwith 3 hole strand mold head at the resin temperature of 310° C. toprepare pellet of PPS resin composition.

The crystallization temperature during cooling, chloroform-extractablecontent, laser transmissivity, heat distortion temperature and, at thesame time, laser weld strength and warpage property of these pellets ofPPS resin composition were evaluated respectively, to obtain resultsshown in Table 4.

Embodiments 53-55

Respective materials from PPS resin group described in (1), glass fibergroup described in (2), silane compound described in (5), antioxidantdescribed in (6), and elastomer group described in (7) mentioned aboveare selected with the combination and quantity described in Table 5,compounded, and pelletized respectively by the double shaft extruder PCMwith 3 hole strand mold head at the resin temperature of 310° C. toprepare pellet of PPS resin composition. The crystallization temperatureduring cooling, chloroform-extractable content, laser transmissivity,heat distortion temperature and, at the same time, laser weld strength,warpage property, and cold and heat resistance of these pellets of PPSresin composition were evaluated respectively, to obtain results shownin Table 5. It should be noted that results of the aforementionedembodiments 5 and 27 are also described in Table 5.

Embodiment 56

Respective materials from PPS resin group described in (1) and glassfiber group described in (2) mentioned above are selected with thecombination and quantity described in Table 4, compounded, andpelletized respectively by the double shaft extruder PCM with 3 holestrand mold head at the resin temperature of 310° to prepare pellet ofPPS resin composition.

Test pieces were injection-molded at the mold temperature of 80°, andthe crystallization temperature during cooling, chloroform-extractablecontent, laser transmissivity, heat distortion temperature and, at thesame time, laser weld strength and warpage property of these pellets ofPPS resin composition were evaluated respectively, to obtain resultsshown in Table 6. It should be noted that results of the aforementionedembodiments 5 and 9 are also described in Table 6.

Embodiments 57-81, Comparative Examples 8-10

Respective materials from PPS resin group described in (1), glass fibergroup described in (2), filler group other than glass fiber described in(3), amorphous resin group described in (4), antioxidant described in(6), and elastomer group described in (7) mentioned above are selectedwith the combination and quantity described in Tables 7-9, compounded,and pelletized respectively by the double shaft extruder PCM with 3 holestrand mold head at the resin temperature of 310° C. to prepare pelletof PPS resin composition.

The crystallization temperature during cooling and, at the same time,laser weld strength, warpage property, heat resistance, and cold andheat resistance of these pellets of PPS resin composition were evaluatedrespectively, to obtain results shown in Table 7 to 9. It should benoted that results of the aforementioned embodiment 31 are alsodescribed in Table 7 and 8.

INDUSTRIAL APPLICABILITY

PPS resin composition of the present invention can be used effectivelyfor laser weld bonding of resin molded products in various applicationssuch as electrical and electronic equipment, precision instrumentconcerning equipment, office equipment, automobile and vehicleconcerning parts, construction material, wrapping material, furniture,daily goods and so on. TABLE 1 Filler equal or Filler less than superiorto 1.6 1.6 or equal or and less than superior to 1.8 Silane Mold Glassfiber 1.8 in reflective in reflective Amorphous compound Antioxidanttempera- PPS resin (parts (parts by index (parts by index (parts byresin (parts (parts by (parts ture by weight) weight) weight) weight) byweight) weight) by weight) (° C.) Embodiment 1 PPS1(100) GF1(30) 130Embodiment 2 PPS2(100) GF1(30) 130 Embodiment 3 PPS3(100) GF1(30) 130Embodiment 4 PPS4(100) GF1(30) 130 Embodiment 5 PPS1(100) GF2(30) 130Embodiment 6 PPS1(100) GF3(30) 130 Embodiment 7 PPS1(100) GF4(30) 130Embodiment 8 PPS1(100) GF1(80) 130 Embodiment 9 PPS1(100) GF3(80) 130Comparative PPS5(100) GF2(30) 130 Example 1 Comparative PPS6(100)GF2(30) 130 Example 2 Comparative PPS7(100) GF2(30) 130 Example 3Comparative PPS1(100) GF5(30) 130 Example 4 Comparative PPS1(100)GF2(200) 130 Example 5 Comparative PPS1(100) 130 Example 6 ComparativePPS1(100) GB2(30) 130 Example 7 Crystalliza-tion Laser weld temperatureChloroform-extractable Heat distortion strength (2.0 mm during coolingcontent Laser permeability temperature thick) Warpage (° C.) (weight %)(%) (° C.) (MPa) property Embodiment 1 190 0.18 20 260 45 D Embodiment 2195 0.25 17 260 40 D Embodiment 3 190 0.25 18 260 42 D Embodiment 4 1900.31 20 245 43 D Embodiment 5 190 0.18 22 260 45 D Embodiment 6 190 0.1827 260 45 D Embodiment 7 190 0.18 30 255 45 D Embodiment 8 192 0.13 16260 40 B Embodiment 9 192 0.13 22 260 45 B Comparative 225 0.31 9 260Not welded D Example 1 Comparative 225 1.54 4 260 Not welded D Example 2Comparative 220 1.85 6 260 Not welded D Example 3 Comparative 190 0.1811 260 30 D Example 4 Comparative 200 0.10 4 260 Not welded B Example 5Comparative 185 0.24 39 105 41 E Example 6 Comparative 190 0.18 27 13543 E Example 7

TABLE 2 Filler equal or Filler less than 1.6 Amor- superior to 1.6 andor equal or superior phous Silane PPS resin Glass fiber less than 1.8 into 1.8 in reflective resin compound Antioxidant Mold (parts by (parts byreflective index index (parts by (parts by (parts by (parts bytemperature weight) weight) (parts by weight) weight) weight) weight)weight) (° C.) Embodiment 10 PPS1(100) GF2(30) GFL(10) 130 Embodiment 11PPS1(100) GF2(30) GB1(10) 130 Embodiment 12 PPS1(100) GF2(30) GB2(10)130 Embodiment 13 PPS1(100) GF2(30) EG(10) 130 Embodiment 14 PPS1(100)GF2(30) HG1(10) 130 Embodiment 15 PPS1(100) GF2(30) HG2(10) 130Embodiment 16 PPS1(100) GF2(30) BM1(10) 130 Embodiment 17 PPS1(100)GF2(30) BM2(10) 130 Embodiment 18 PPS1(100) GF2(30) BM3(10) 130Embodiment 19 PPS1(100) GF2(20) GFL(10)/GB2 130 (10) Embodiment 20PPS1(100) GF2(20) HG2(10)/BM3 130 (10) Embodiment 21 PPS1(100) GF2(20)BM3(10) GB2(10) 130 Embodiment 22 PPS1(100) GF2(30) PAI(5) 130Embodiment 23 PPS1(100) GF2(30) PAI(20) 130 Embodiment 24 PPS1(100)GF2(30) PEI(5) 130 Embodiment 25 PPS1(100) GF2(30) PES(5) 130 Embodiment26 PPS1(100) GF2(30) PSU(5) 130 Laser Crystalliza-tion depositiontemperature Chloroform-extractable Heat distortion strength duringcontent Laser permeability temperature (2.0 mm Warpage cooling (° C.)(weight %) (%) (° C.) thick) (MPa) property Embodiment 10 190 0.17 18260 42 A Embodiment 11 190 0.17 16 260 40 C Embodiment 12 190 0.17 18260 42 C Embodiment 13 190 0.17 16 260 40 C Embodiment 14 190 0.17 18260 42 C Embodiment 15 190 0.17 20 260 45 C Embodiment 16 190 0.17 18260 42 B Embodiment 17 190 0.17 20 260 45 B Embodiment 18 190 0.17 19260 42 B Embodiment 19 190 0.17 16 260 40 A Embodiment 20 190 0.17 19260 42 B Embodiment 21 190 0.17 18 260 42 B Embodiment 22 191 0.22 25260 45 B Embodiment 23 191 0.25 25 260 45 A Embodiment 24 189 0.22 23260 45 B Embodiment 25 189 0.22 23 260 45 B Embodiment 26 189 0.24 23260 45 B

TABLE 3 Filler less Filler equal or than 1.6 or superior to equal or 1.6and less superior to than 1.8 in 1.8 in Amorphous Silane Glass fiberreflective reflective resin compound Antioxidant Mold PPS resin (parts(parts by index (parts index (parts (parts by (parts by (parts bytemperature by weight) weight) by weight) by weight) weight) weight)weight) (° C.) Embodiment 5 PPS1(100) GF2(30) 130 Embodiment 27PPS1(100) GF2(30) 0.2 130 Embodiment 28 PPS1(100) GF2(30) 0.5 130Embodiment 29 PPS1(100) GF2(30) 0.2 0.5 130 Embodiment 30 PPS1(100)GF2(30) PAI(5) 0.2 0.5 130 Crystallization Laser weld temperatureChloroform-extractable Heat distortion strength (3.5 mm during contentLaser permeability temperature thick) Warpage cooling (° C.) (weight %)(%) (° C.) (MPa) property Embodiment 5 190 0.18 22 260 42 D Embodiment27 188 0.18 24 260 45 D Embodiment 28 190 0.18 24 260 45 D Embodiment 29188 0.18 25 260 45 D Embodiment 30 189 0.22 27 260 45 B

TABLE 4 Filler equal or superior to 1.6 Filler less than and less than1.8 1.6 or equal or Amorphous Glass fiber in reflective superior to 1.8in resin Silane compound PPS resin (parts (parts by index (parts byreflective index (parts by (parts by Antioxidant by weight) weight)weight) (parts by weight) weight) weight) (parts by weight) Embodiment31 PPS1(100) GF3(60) Embodiment 6 PPS1(100) GF3(30) Embodiment 32PPS1(100) GF3(30) GFL(10) Embodiment 33 PPS1(100) GF3(30) GB1(10)Embodiment 34 PPS1(100) GF3(30) GB2(10) Embodiment 35 PPS1(100) GF3(30)EG(10) Embodiment 36 PPS1(100) GF3(30) HG1(10) Embodiment 37 PPS1(100)GF3(30) HG2(10) Embodiment 38 PPS1(100) GF3(30) BM1(10) Embodiment 39PPS1(100) GF3(30) BM2(10) Embodiment 40 PPS1(100) GF3(30) BM3(10)Embodiment 41 PPS1(100) GF3(20) GFL(10)/ GB2(10) Embodiment 42 PPS1(100)GF3(20) HG2(10)/ BM3(10) Embodiment 43 PPS1(100) GF3(20) BM3(10) GB2(10)Embodiment 44 PPS1(100) GF3(30) PAI(5) Embodiment 45 PPS1(100) GF3(30)PAI(20) Embodiment 46 PPS1(100) GF3(30) PEI(5) Embodiment 47 PPS1(100)GF3(30) PES(5) Embodiment 48 PPS1(100) GF3(30) PSU(5) Embodiment 49PPS1(100) GF3(30) 0.2 Embodiment 50 PPS1(100) GF3(30) 0.5 Embodiment 51PPS1(100) GF3(30) 0.2 0.5 Embodiment 52 PPS1(100) GF3(30) PAI(5) 0.2 0.5Crystallization Chloroform Laser weld Mold temperature extraction Heatdistortion strength temperature during cooling quantity Laserpermeability temperature (4.5 mm thick) Warpage (° C.) (° C.) (weight %)(%) (° C.) MPa) property Embodiment 31 130 191 0.15 24 260 38 BEmbodiment 6 130 190 0.18 27 260 40 D Embodiment 32 130 190 0.17 23 26037 A Embodiment 33 130 190 0.17 21 260 33 C Embodiment 34 130 190 0.1723 260 37 C Embodiment 35 130 190 0.17 21 260 33 C Embodiment 36 130 1900.17 23 260 37 C Embodiment 37 130 190 0.17 25 260 39 C Embodiment 38130 190 0.17 23 260 37 B Embodiment 39 130 190 0.17 25 260 39 BEmbodiment 40 130 190 0.17 24 260 37 B Embodiment 41 130 190 0.17 21 26033 A Embodiment 42 130 190 0.17 24 260 37 B Embodiment 43 130 190 0.1723 260 37 B Embodiment 44 130 191 0.22 30 260 43 B Embodiment 45 130 1910.25 30 260 43 A Embodiment 46 130 189 0.22 28 260 41 B Embodiment 47130 189 0.22 28 260 41 B Embodiment 48 130 189 0.24 28 260 41 BEmbodiment 49 130 188 0.18 29 260 42 D Embodiment 50 130 190 0.18 29 26042 D Embodiment 51 130 188 0.16 30 260 43 D Embodiment 52 130 189 0.2232 260 44 B

TABLE 5 Silane Crystallization Glass fiber compound Antioxidanttemperature PPS resin (parts (parts by (parts by (parts by Elastomer(parts Mold temperature during cooling by weight) weight) weight)weight) by weight) (° C.) (° C.) Embodiment 5 PPS1(100) GF2(30) 130 190Embodiment 27 PPS1(100) GF2(30) 0.2 130 188 Embodiment 53 PPS2(100)GF2(30) ER1(1.5) 130 189 Embodiment 54 PPS1(100) GF2(80) 130 192Embodiment 55 PPS1(100) GF2(30) 0.2 0.5 ER1(1.5)/ 130 187 ER2(1.5) LaserChloroform-extractable Heat distortion weld strength Thermal shockcontent Laser permeability temperature (2.0 mm thick) Warpage resistance(weight %) (%) (° C.) (MPa) property (cycle) Embodiment 5 0.18 22 260 45D D Embodiment 27 0.18 24 260 45 D C Embodiment 53 0.3 17 260 40 D BEmbodiment 54 0.13 18 260 42 B C Embodiment 55 0.44 15 260 34 D A

TABLE 6 Crystallization PPS resin Glass fiber Mold temperature Laser(parts by (parts by temperature during cooling Chloroform-extractablepermeability weight) weight) (° C.) (° C.) content (weight %) (%)Embodiment 5 PPS1(100) GF2(30) 130 190 0.18 22 Embodiment 9 PPS1(100)GF3(80) 130 192 0.13 22 Embodiment 56 PPS2(100) GF3(80) 80 192 0.13 8Laser weld Laser weld Heat distortion strength (2.0 mm strength (2.0 mmtemperature thick) thick) Warpage (° C.) (MPa) (MPa) property Embodiment5 260 44 42 D Embodiment 9 260 42 37 B Embodiment 56 260 47 41 B

TABLE 7 PPS resin Antioxidant Elastomer (parts by Filler (parts byAmorphous resin (parts by (parts by Mold temperature weight) weight)(parts by weight) weight) weight) (° C.) Embodiment 31 PPS1(100) GF3(60)— — — 130 Embodiment 57 PPS1(100) GF4(60) — — — 130 Embodiment 58PPS1(100) GF4(45)/GB1 (15) — — — 130 Embodiment 59 PPS1(100) GF4(45)/GB2(15) — — — 130 Embodiment 60 PPS1(100) GF4(45)/EG (15) — — — 130Embodiment 61 PPS1(100) GF4(45)/HG1 — — — 130 (15) Embodiment 62PPS1(100) GF4(45)/HG2 — — — 130 (15) Embodiment 63 PPS1(100) GF4(45)/BM1(15) — — — 130 Embodiment 64 PPS1(100) GF4(45)/BM2 (15) — — — 130Embodiment 65 PPS1(100) GF4(20) — — — 130 Embodiment 66 PPS1(100)GF4(45) — — — 130 Embodiment 67 PPS1(100) GF4(100) — — — 130 Embodiment68 PPS1(100) GF4(45) PAI(15) — — 130 Embodiment 69 PPS1(100) GF4(45)PAI(85) — — 130 Embodiment 70 PPS1(100) GF4(45) PAI(100) — — 130Embodiment 71 PPS1(100) GF4(45) PAR(15) — — 130 Embodiment 72 PPS1(100)GF4(45) PES(15) — — 130 Embodiment 73 PPS1(100) GF4(45) PEI(15) — — 130Embodiment 74 PPS1(100) GF4(45) PSU(15) — — 130 Embodiment 75 PPS1(100)GF4(45) PAI(15) 0.3 — 130 Embodiment 76 PPS1(100) GF4(45) PAI(15) 0.3ER-1(5) 130 Embodiment 77 PPS1(100) GF4(45) PAI(15) 0.3 ER-1(2)/ER-2 130(3) Embodiment 78 PPS1(100) GF4(45) PAI(15) 0.3 ER-1(3)/ER.2 130 (4)Embodiment 79 PPS1(100) GF4(15)/BM2 (5) PAI(15) 0.3 ER-1(1)/ER-2 130 (1)Embodiment 80 PPS1(100) GF4(30)/BM2 (15) PAI(15) 0.3 ER-1(1)/ER-2 130(1) Embodiment 81 PPS1(100) GF4(40)/BM2 (20) PAI(15) 0.3 ER-1(1)/ER-2130 (1) Comparative PPS5(100) GF4(20) — — — 130 Example 8 ComparativePPS6(100) GF4(20) — — — 130 Example 9 Comparative PPS7(100) GF4(20) — —— 130 Example 10 Laser weld Crystallization strength (4.5 mm temperatureduring thick) Warpage Heat cooling (° C.) (MPa) property resistanceEmbodiment 31 190 38 B 260 Embodiment 57 190 40 B 260 Embodiment 58 19038 B 260 Embodiment 59 190 43 B 260 Embodiment 60 190 37 B 260Embodiment 61 190 39 B 260 Embodiment 62 190 42 B 260 Embodiment 63 19039 A 260 Embodiment 64 190 40 A 260 Embodiment 65 188 49 D 250Embodiment 66 189 44 C 260 Embodiment 67 193 31 A 260 Embodiment 68 19147 B 260 Embodiment 69 191 48 A 260 Embodiment 70 191 40 A 260Embodiment 71 189 46 B 260 Embodiment 72 189 46 B 260 Embodiment 73 18946 B 260 Embodiment 74 189 46 B 260 Embodiment 75 191 49 B 260Embodiment 76 190 37 B 260 Embodiment 77 190 37 B 260 Embodiment 78 19030 B 255 Embodiment 79 190 47 A 255 Embodiment 80 190 43 A 260Embodiment 81 192 39 A 260 Comparative 225 Not welded D 250 Example 8Comparative 225 Not welded D 250 Example 9 Comparative 220 Not welded D250 Example 10

TABLE 8 Laser weld PPS resin Amorphous Antioxidant Mold strength (5.0 mm(parts by Filler resin (parts by (parts by Elastomer (parts bytemperature thick) weight) (parts by weight) weight) weight) weight) (°C.) (MPa) Embodiment 31 PPS1(100) GF3(60) — — — 130 30 Embodiment 57PPS1(100) GF4(60) — — — 130 32 Embodiment 58 PPS1(100) GF4(45)/GB1(15) —— — 130 30 Embodiment 59 PPS1(100) GF4(45)/GB2(15) — — — 130 35Embodiment 61 PPS1(100) GF4(45)/HG1(15) — — — 130 31 Embodiment 62PPS1(100) GF4(45)/HG2(15) — — — 130 34 Embodiment 63 PPS1(100)GF4(45)/BM1(15) — — — 130 31 Embodiment 64 PPS1(100) GF4(45)/BM2(15) — —— 130 32 Embodiment 65 PPS1(100) GF4(20) — — — 130 41 Embodiment 66PPS1(100) GF4(45) — — — 130 36 Embodiment 68 PPS1(100) GF4(45) PAI(15) —— 130 39 Embodiment 69 PPS1(100) GF4(45) PAI(65) — — 130 40 Embodiment70 PPS1(100) GF4(45) PAI(100) — — 130 32 Embodiment 71 PPS1(100) GF4(45)PAR(15) — — 130 38 Embodiment 72 PPS1(100) GF4(45) PES(15) — — 130 38Embodiment 73 PPS1(100) GF4(45) PEI(15) — — 130 38 Embodiment 74PPS1(100) GF4(45) PSU(15) — — 130 38 Embodiment 75 PPS1(100) GF4(45)PAI(15) 0.3 — 130 41 Embodiment 79 PPS1(100) GF4(15)/BM2(5) PAI(15) 0.3ER-1(1)/ER-2(1) 130 39 Embodiment 80 PPS1(100) GF4(30)/BM2(15) PAI(15)0.3 ER-1(1)/ER-2(1) 130 35 Embodiment 81 PPS1(100) GF4(40)/BM2(20)PAI(15) 0.3 ER-1(1)/ER-2(1) 130 31 Comparative PPS5(100) GF4(20) — — —130 Not welded Example 8 Comparative PPS6(100) GF4(20) — — — 130 Notwelded Example 9 Comparative PPS7(100) GF4(20) — — — 130 Not weldedExample 10

TABLE 9 Thermal PPS resin Amorphous Antioxidant shock (parts by Filler(parts by resin (parts by (parts by Elastomer (parts resistance weight)weight) weight) weight) by weight) (cycle) Embodiment PPS1(100) GF4(45)PAI(15) 0.3 — D 75 Embodiment PPS1(100) GF4(45) PAI(15) 0.3 ER-1(5) B 76Embodiment PPS1(100) GF4(45) PAI(15) 0.3 ER-1(2)/ER-2(3) A 77 EmbodimentPPS1(100) GF4(45) PAI(15) 0.3 ER-1(3)/ER-2(4) A 78 Embodiment PPS1(100)GF4(15)/BM2(5) PAI(15) 0.3 ER-1(1)/ER-2(1) D 79 Embodiment PPS1(100)GF4(30)/BM2(15) PAI(15) 0.3 ER-1(1)/ER-2(1) B 80 Embodiment PPS1(100)GF4(40)/BM2(20) PAI(15) 0.3 ER-1(1)/ER-2(1) A 81 Comparative PPS5(100)GF4(20) — — — D Example 8 Comparative PPS6(100) GF4(20) — — — D Example9 Comparative PPS7(100) GF4(20) — — — E Example 10

1. A polyphenylene sulfide resin composition which comprises 100 partsby weight of a polyphenylene sulfide resin (A) and, compoundedtherewith, 1 to 100 parts by weight of glass fiber (B) having amonofilament diameter of about 12 μm or larger, and has acrystallization temperature during cooling of about 205° C. or less. 2.The polyphenylene sulfide resin composition of claim 1, having achloroform-extractable content of about 0.5 wt. % or less, and giving a2 mm-thick molded product which has a transmittance of about 15% or morefor a laser beam having a wavelength of 940 nm and a heat distortiontemperature of about 230° C. or more under a load of 1.82 MPa.
 3. Apolyphenylene sulfide resin composition, comprising 100 parts by weightof a polyphenylene sulfide resin (A) and, compounded therewith, 1 to 100parts by weight of glass fiber (B) having a monofilament diameter ofabout 10 μm or more, but less than about 12 μm and having acrystallization temperature during cooling of about 205° C. or less, andhaving a chloroform-extractable content of about 0.5 wt. % or less andgiving a 2 mm-thick molded product which has a transmittance of about15% or more for a laser beam having a wavelength of 940 nm and a heatdistortion temperature of about 230° C. or more under a load of 1.82MPa.
 4. The polyphenylene-sulfide resin composition of claim 1 or 2,wherein the glass fiber has a monofilament diameter of 15 μm or larger.5. The polyphenylene-sulfide resin composition of claim 1 or 3, whichcompounds 1 to 200 parts by weight of a filler(C) having a refractiveindex of about 1.6 to about 1.8 and/or a filler (D) having a refractiveindex of less than about 1.6 or more than about 1.8 and an averageparticle diameter of about 30 μm or more.
 6. The polyphenylene-sulfideresin composition of claim 5, wherein the filler (C) is fibrous orplate-shaped alumina hydrate (C1), and/or fibrous or granular H glass(C2) other than the component (B).
 7. The polyphenylene-sulfide resincomposition of claim 5, wherein the filler (D) is glass flake (D1)and/or glass beads (D2).
 8. The polyphenylene-sulfide resin compositionof claim 1 or 3 which comprises 100 parts by weight of a polyphenylenesulfide resin (A) and, further compounded therewith, 0.1 to 200 parts byweight of one or more amorphous resin selected from polyamide-imideresin (E1), polyether-imide resin (E2), polyethersulfone resin (E3) andpolysulfone resin (E4).
 9. The polyphenylene-sulfide resin compositionof claim 1 or 3 which comprises 100 parts by weight of a polyphenylenesulfide resin (A) and, further compounded therewith, 0.01 to 3 parts byweight of silane compound (F) and/or 0.01 to 3 parts by weight oantioxidant (G).
 10. The polyphenylene-sulfide resin composition ofclaim 1 or 3 which comprises 100 parts by weight of a polyphenylenesulfide resin (A) and, further compounded therewith, 0.5 to 20 parts byweight of elastomer (H).
 11. A polyphenylene-sulfide resin compositionmolded product comprising the polyphenylene sulfide resin composition ofclaim 1 or 3, and has a thickness of a transmission part of a weldingsite of about 3 mm or less to be used at a laser beam transmission side.12. A method for manufacturing of polyphenylene sulfide resincomposition molded product comprising injection molding thepolyphenylene sulfide resin composition of claim 1 or 3 into a mold at amold temperature of about 100° C. or less.
 13. A polyphenylene sulfideresin composition composite molded product obtained by laser welding thepolyphenylene-sulfide resin composition of claim 1 or 3 to another resinmolded product.
 14. The polyphenylene sulfide resin compositioncomposite molded product of claim 13, wherein another resin moldedproduct comprises polyphenylene sulfide resin.
 15. A method formanufacturing of polyphenylene sulfide resin composition compositemolded product comprising laser welding the polyphenylene sulfide resincomposition of claim 1 or 3 to another resin molded product, andheat-treating the composite molded product.